CN106905504A - UV-curable waterborne polyurethane resin and its preparation method and application - Google Patents
UV-curable waterborne polyurethane resin and its preparation method and application Download PDFInfo
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- CN106905504A CN106905504A CN201710176972.XA CN201710176972A CN106905504A CN 106905504 A CN106905504 A CN 106905504A CN 201710176972 A CN201710176972 A CN 201710176972A CN 106905504 A CN106905504 A CN 106905504A
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The present invention relates to a kind of UV-curable waterborne polyurethane resin and its preparation method and application.The UV-curable waterborne polyurethane resin, in parts by weight, including the following raw material component:25~40 parts of diisocyanate, 1~5 part of castor oil, 20~30 parts of polyalcohol, 5~10 parts of epoxy acrylate, 2,2 5~10 parts of dihydromethyl propionic acids, 10~15 parts of pentaerythritol triacrylate, 1~5 part of 1,4 butanediol, 0.0057~0.006 part of catalyst, 0.002~0.005 part of polymerization inhibitor, 0.004~0.005 part of end-capping reagent.UV-curable waterborne polyurethane resin of the invention, it is used as raw material components by using specific monomer, obtained resin can be made have that photo-curing rate is fast, production efficiency is high, gloss is high after curing of coating, hardness is high, the advantages of adhesive force, pliability are good, excellent combination property.
Description
Technical field
The present invention relates to macromolecular material, more particularly to a kind of UV-curable waterborne polyurethane resin and its preparation side
Method and application.
Background technology
In recent years, as the whole world is to the attention of environmental protection and the development of green chemical technology, various countries start to VOC content
Limitation, UV-curable waterborne polyurethane resin (aqueous UV polyurethane resins) is to substitute organic solvent using water to be situated between as dispersion
Matter, with the obvious value of environmental protection, and have that curing rate is fast using UV-curing technology, can operate at room temperature, consume energy it is low,
The advantages of coating performance is excellent.Aqueous UV polyurethane resins can apply to coating, adhesive, aqueous leather finishing agent, fabric
The aspects such as finishing agent, are increasingly valued by people.
However, existing UV-curable waterborne polyurethane resin at present, it is difficult to take into account superior mechanical performance and good
Water resistance, solvent resistance, and there is the shortcomings of crosslink density is low, photo-curing rate is slow.And, aqueous purple is such as applied merely
Outer light-cured polyurethane resin, also has that weatherability, heat resistance be poor, the low shortcoming of adhesive strength, thus limit aqueous
The promotion and application of ultraviolet curing urethane resin.
The content of the invention
Based on this, it is necessary to provide that a kind of solid content is high, photo-curing rate fast, gloss, hardness, attachment after curing of coating
The UV-curable waterborne polyurethane resin of the excellent combination property such as power, pliability, water-fast, solvent resistant.
A kind of UV-curable waterborne polyurethane resin, in parts by weight, including the following raw material component:
UV-curable waterborne polyurethane resin of the invention, raw material components are used as by using specific monomer, can
Obtained resin is set to have that solid content is high, photo-curing rate is fast, production efficiency is high, gloss is high after film, hardness is high, adhesive force,
The advantages of pliability is good.Its principle is as follows:
First, the present invention is comprehensive is modified with castor oil using epoxy acrylate to waterborne polyurethane resin.Wherein,
Epoxy acrylate has the advantages of epoxy resin modulus is high, intensity is high and chemical resistance is good, heat endurance is good, and acrylic acid concurrently
The preferable water resistance of ester, physics characteristic and weather resistance and it is with low cost the characteristics of.Castor oil is then a kind of reproducible plant
Thing oil, abundance.The main component of castor oil is the triglyceride of higher fatty acids, and 80%~90% is castor in aliphatic acid
Sesame oil is sour (hydroxy octadecadienoic acid of 9- alkenyls -12), castor oil hydroxyl value 163mgKOH/g, hydroxyl 4.94%, and hydroxyl moles are
345.Calculated according to hydroxyl value, containing 70% three-functionality-degree and 30% two degrees of functionality, hydroxyl average functionality is 2.7 to castor oil,
This specific structure of castor oil can make its in the synthesis of polyurethane resin can as soft section, increase pliability, and
Crosslinking agent can be played a part of, the degree of cross linking of polyurethane resin is improved, water-fast, the performance such as solvent resistant and mechanics of paint film is improved.
In addition the side chain of castor oil also contains substantial amounts of unsaturated carbon-carbon double bond, can provide active site for its further graft modification,
Further improve the performance of film.
Secondly, on the basis of foregoing polyurethane resin, 2,2- dihydromethyl propionic acids are introduced, prepares carboxylic polyurethane
Prepolymer, then introduces pentaerythritol triacrylate in end group again, prepares the watersoluble polyurethane acrylic acid of multiple double bond end-blocking
Ester, thus greatly improves the double bond content in system, it is ensured that the laser curing velocity and production efficiency of resin.Meanwhile, resin has
Solid content higher, it is possible to reduce the time of the complicated technology such as heat drying or infra-red drying, improve production efficiency after resin coating film.
Wherein in one embodiment, the UV-curable waterborne polyurethane resin, in parts by weight, including the following raw material
Component:
Wherein in one embodiment, the molecular weight of the polyalcohol is 500~1500g/mol.
Wherein in one embodiment, the polyalcohol is polyether Glycols, PTMG dihydroxylic alcohols, polycaprolactone
One or more in dihydroxylic alcohols, PCDL.
Wherein in one embodiment, the diisocyanate is isophorone diisocyanate, diphenylmethane diisocyanates
One kind or many in ester, dicyclohexyl methyl hydride diisocyanate, toluene di-isocyanate(TDI), 1,6- hexamethylene diisocyanates
Kind.
Wherein in one embodiment, the molecular weight of the epoxy acrylate is 450~460g/mol, and solid content is
100%.
Wherein in one embodiment, the polymerization inhibitor be 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radicals,
One or more in 2,2,6,6- tetramethyl piperidine -1- oxygen radicals, hydroquinones;The end-capping reagent is monohydric alcohol.It is preferred that
It is methyl alcohol and/or absolute ethyl alcohol.
Wherein in one embodiment, also including the tertiary amine that weight portion is 4~5 parts, preferably triethylamine or triethanolamine,
And the water with 6~8 parts.Tertiary amine and water are further added in resin, emulsifying salt can be carried out into, it is possible to increase the storage of resin
Deposit stability.
The present invention also provides the preparation method of described UV-curable waterborne polyurethane resin, comprises the following steps:
(1) preparation of carboxylic base polyurethane prepolymer for use as:
Castor oil and partial catalyst are added in the diisocyanate, 1.5~2h is reacted in 45~55 DEG C;
Then added in reaction solution and be dissolved with the polyalcohol of the remaining catalyst, be warming up to 75~80 DEG C of reactions 2~
2.5h;
Then 40~50 DEG C are cooled to, the BDO and epoxy acrylate are added in reaction solution, then heat up
To 70~75 DEG C of reactions 1~1.5;
Then 40~50 DEG C are cooled to, described, 2- dihydromethyl propionic acids are added in reaction solution, then be warming up to 70~75 DEG C
2~2.5h of reaction, obtains the carboxylic base polyurethane prepolymer for use as;
(2) preparation of UV-curable waterborne polyurethane resin:
After the carboxylic base polyurethane prepolymer for use as is cooled into 40~50 DEG C, is added in reaction solution and be dissolved with the resistance
The pentaerythritol triacrylate of poly- agent, is warming up to 60~70 DEG C of 2~3h of reaction;
The end-capping reagent is subsequently adding, after NCO content is less than 0.2wt%, terminating reaction obtains final product the aquosity ultraviolet light
Curable polyurethane resin.
Wherein in one embodiment, in step (2), after NCO content is less than 0.2wt%, reactant is cooled to
Less than 40 DEG C, the tertiary amine and water is added to carry out into emulsifying salt.
Wherein in one embodiment, the method into emulsifying salt is:In stirring under 1100~1300r/min speed
0.5~1h, pH value is controlled 6~8.
The present invention also provides a kind of aqueous polyurethane coating, by weight percentage, including following component:
Compared with prior art, the invention has the advantages that:
1st, UV-curable waterborne polyurethane resin of the invention, raw material components, energy are used as by using specific monomer
Enough make obtained resin and have that photo-curing rate is fast, production efficiency is high, gloss is high after curing of coating, hardness is high, it is adhesive force, flexible
The advantages of property is good, excellent combination property.
2nd, UV-curable waterborne polyurethane resin of the invention, with solid content higher, can be after resin coating film
Reduce the time of the complicated technologies such as heat drying or infra-red drying, improve production efficiency.
3rd, the preparation method of UV-curable waterborne polyurethane resin of the invention, process is simple is easy to operate, and during
Substantial amounts of organic solvent need not be added, with good environment protection significance.
Specific embodiment
Below in conjunction with specific embodiment is to UV-curable waterborne polyurethane resin of the invention and preparation method thereof and answers
With being described in further detail.
Embodiment 1
A kind of UV-curable waterborne polyurethane resin of the present embodiment, its raw material and preparation method are as follows:
1) under nitrogen protection, 28 parts of toluene di-isocyanate(TDI)s are placed in equipped with mechanical agitator, dropping funel and backflow
In the four-hole boiling flask of condenser pipe, 30~40 DEG C are warming up to, start that 2 parts of castor oil and 0.0004 part of di lauric dibutyl is added dropwise
Tin, 1.5~2h is reacted after dripping off at 50 ± 2 DEG C.
2) at being 50~55 DEG C in temperature, it is added dropwise dissolved with 0.0056 part of the 28 of dibutyl tin laurate parts of makrolon two
First alcohol (molecular weight is 1000g/mol), is dripped in 1h, and 75~80 DEG C are warming up to after dripping off, and reacts 2~2.5h;
3) 40~50 DEG C are cooled to, 3 parts of BDOs and 6 parts of epoxy acrylates dissolved with a small amount of acetone is added dropwise,
Completion of dropping in 1h.Rise high-temperature to 70~75 DEG C of 1~1.5h of reaction.
4) 40~50 DEG C are cooled to, then 7 parts of 2,2- dihydromethyl propionic acids (DMPA) are dissolved in a small amount of 1-METHYLPYRROLIDONE,
Disposably it is added directly into reactor, rises high-temperature to 70~75 DEG C of 2~2.5h of reaction, it is a small amount of by adding in course of reaction
Acetone obtains carboxylic base polyurethane prepolymer for use as to control the viscosity of reaction system.
5) 40~50 DEG C are cooled to, while stirring toward step 4) be added dropwise in performed polymer dissolved with polymerization inhibitor (4- hydroxyl -2,2,6,
6- tetramethyl piperidine -1- oxygen radicals, 0.004 part) 14 parts of pentaerythritol triacrylates (PETA), dripped in 1h;
Be warming up to 60~70 DEG C after dripping, added after 2~3h of reaction 0.0045 part of small molecule monohydric alcohol (methyl alcohol) end capping reaction 0.5~
1h, then determines the content (use di-n-butylamine method) of isocyano, and terminating reaction after-NCO content is less than 0.2wt.% is obtained
The castor oil and epoxy polyurethane modified urethane acrylate performed polymer of unsaturated acrylate ended.
6) less than 40 DEG C are cooled to, toward step 5) add in performed polymer 5 parts of triethylamines and the 7 parts of deionized waters to carry out into salt breast
Change, 1h is reacted under 1200r/min speed and obtains castor oil and epoxy polyurethane modified water-soluble UV resins, pH value is controlled 7.0
Left and right, its solid content is 83%.
In above-mentioned steps, the component is required to strict water removal.
Embodiment 2
A kind of UV-curable waterborne polyurethane resin of the present embodiment, its raw material and preparation method are as follows:
1) under nitrogen protection, 36 parts of dicyclohexyl methyl hydride diisocyanates are placed in and are leaked equipped with mechanical agitator, dropping liquid
In the four-hole boiling flask of bucket and reflux condensing tube, 30~40 DEG C are warming up to, start that 1 part of castor oil and 0.0002 part of tin dilaurate is added dropwise
Dibutyl tin, 1.5~2h is reacted after dripping off at 50 ± 2 DEG C.
2) at being 50~55 DEG C in temperature, molten 0.0057 part 23 parts of polyether Glycols for having dibutyl tin laurate are added dropwise
(molecular weight is 1000g/mol), is dripped in 1h, and 75~80 DEG C are warming up to after dripping off, and reacts 2~2.5h.
3) 40~50 DEG C are cooled to, 3 parts of BDOs and 5 parts of epoxy acrylates dissolved with a small amount of acetone is added dropwise,
Completion of dropping in 1h.Rise high-temperature to 70~75 DEG C of 1~1.5h of reaction.
4) 40~50 DEG C are cooled to, then 6 parts of 2,2- dihydromethyl propionic acids (DMPA) are dissolved in a small amount of 1-METHYLPYRROLIDONE,
Disposably it is added directly into reactor, rises high-temperature to 70~75 DEG C of 2~2.5h of reaction, it is a small amount of by adding in course of reaction
Acetone obtains carboxylic base polyurethane prepolymer for use as to control the viscosity of reaction system.
5) 40~50 DEG C are cooled to, while stirring toward being added dropwise dissolved with polymerization inhibitor (2,2,6,6- tetramethyls in above-mentioned performed polymer
Piperidines -1- oxygen radicals, 0.003 part) 12 parts of pentaerythritol triacrylates (PETA), dripped in 1h;After dripping
60~70 DEG C are warming up to, 0.0045 part of small molecule monohydric alcohol (absolute ethyl alcohol) 0.5~1h of end capping reaction are added after 2~3h of reaction,
Then the content (use di-n-butylamine method) of isocyano is determined, terminating reaction after-NCO content is less than 0.2wt.% is obtained not
The castor oil and epoxy polyurethane modified urethane acrylate performed polymer of saturation acrylate ended.
6) less than 40 DEG C are cooled to, add 4 parts of triethylamines and 9 parts of deionized waters to carry out into salt breast toward above-mentioned performed polymer
Change, stirring reaction 1h obtains castor oil and epoxy polyurethane modified water-soluble UV resins under 1100r/min speed, pH value control exists
7.0 or so, its solid content is 84%.
In above-mentioned steps, the component is required to strict water removal.
Embodiment 3
A kind of UV-curable waterborne polyurethane resin of the present embodiment, its raw material and preparation method are as follows:
1) under nitrogen protection, 28 parts of toluene di-isocyanate(TDI)s are placed in equipped with mechanical agitator, dropping funel and backflow
In the four-hole boiling flask of condenser pipe, 30~40 DEG C are warming up to, start that 2 parts of castor oil and 0.0004 part of di lauric dibutyl is added dropwise
Tin, 1.5~2h is reacted after dripping off at 50 ± 2 DEG C.
2) at being 50~55 DEG C in temperature, molten 0.0054 part 28 parts of PolyTHFs for having dibutyl tin laurate are added dropwise
Dihydroxylic alcohols (molecular weight is 1000g/mol), is dripped in 1h, and 75~80 DEG C are warming up to after dripping off, and reacts 2~2.5h;
3) 40~50 DEG C are cooled to, 3 parts of BDOs and 6 parts of epoxy acrylates dissolved with a small amount of acetone is added dropwise,
Completion of dropping in 1h.Rise high-temperature to 70~75 DEG C of 1~1.5h of reaction.
4) 40~50 DEG C are cooled to, then 7 parts of 2,2- dihydromethyl propionic acids (DMPA) are dissolved in a small amount of 1-METHYLPYRROLIDONE,
Disposably it is added directly into reactor, rises high-temperature to 70~75 DEG C of 2~2.5h of reaction, it is a small amount of by adding in course of reaction
Acetone obtains carboxylic base polyurethane prepolymer for use as to control the viscosity of reaction system.
5) 40~50 DEG C are cooled to, while stirring toward being added dropwise dissolved with polymerization inhibitor (4- hydroxyl -2,2,6,6- in above-mentioned performed polymer
Tetramethyl piperidine -1- oxygen radicals, 0.005 part) 14 parts of pentaerythritol triacrylates (PETA), dripped in 1h;Drop
60~70 DEG C are warming up to after adding, 0.004 part of small molecule monohydric alcohol (methyl alcohol) 0.5~1h of end capping reaction are added after 2~3h of reaction,
Then the content (use di-n-butylamine method) of isocyano is determined, terminating reaction after-NCO content is less than 0.2wt.% is obtained not
The castor oil and epoxy polyurethane modified urethane acrylate performed polymer of saturation acrylate ended.
6) less than 40 DEG C are cooled to, add 5 parts of triethylamines and 7 parts of deionized waters to carry out into salt breast toward above-mentioned performed polymer
Change, stirring reaction 1h obtains castor oil and epoxy polyurethane modified water-soluble UV resins under 1300r/min speed, pH value control exists
7.0 or so, its solid content is 82%.
In above-mentioned steps, the component is required to strict water removal.
Embodiment 4
A kind of UV-curable waterborne polyurethane resin of the present embodiment, its raw material and preparation method are as follows:
1) under nitrogen protection, by 33 parts of IPDIs be placed in equipped with mechanical agitator, dropping funel and
In the four-hole boiling flask of reflux condensing tube, 30~40 DEG C are warming up to, start that 2 parts of castor oil and 0.0004 part of fourth of tin dilaurate two is added dropwise
Ji Xi, 1.5~2h is reacted after dripping off at 50 ± 2 DEG C.
2) at being 50~55 DEG C in temperature, molten 0.0055 part 25 parts of polycaprolactones two for having dibutyl tin laurate are added dropwise
First alcohol (molecular weight is 1000g/mol), is dripped in 1h, and 75~80 DEG C are warming up to after dripping off, and reacts 2~2.5h.
3) 40~50 DEG C are cooled to, 3 parts of BDOs and 5 parts of epoxy acrylates dissolved with a small amount of acetone is added dropwise,
Completion of dropping in 1h.Rise high-temperature to 70~75 DEG C of 1~1.5h of reaction.
4) 40~50 DEG C are cooled to, then 6 parts of 2,2- dihydromethyl propionic acids (DMPA) are dissolved in a small amount of 1-METHYLPYRROLIDONE,
Disposably it is added directly into reactor, rises high-temperature to 70~75 DEG C of 2~2.5h of reaction, it is a small amount of by adding in course of reaction
Acetone obtains carboxylic base polyurethane prepolymer for use as to control the viscosity of reaction system.
5) 40~50 DEG C are cooled to, while stirring toward being added dropwise dissolved with polymerization inhibitor (hydroquinones, 0.002 in above-mentioned performed polymer
Part) 13 parts of pentaerythritol triacrylates (PETA), dripped in 1h;It is warming up to 60~70 DEG C after dripping, reaction 2~
0.005 part of small molecule monohydric alcohol (absolute ethyl alcohol) 0.5~1h of end capping reaction is added after 3h, the content of isocyano is then determined
(using di-n-butylamine method), terminating reaction after-NCO content is less than 0.2wt.%, obtains the castor-oil plant of unsaturated acrylate ended
Oil and epoxy polyurethane modified urethane acrylate performed polymer.
6) less than 40 DEG C are cooled to, add 6 parts of triethylamines and 6 parts of deionized waters to carry out into salt breast toward above-mentioned performed polymer
Change, stirring reaction 1h obtains castor oil and epoxy polyurethane modified water-soluble UV resins under 1100r/min speed, pH value control exists
7.0 or so, its solid content is 83%.
In above-mentioned steps, the component is required to strict water removal.
Embodiment 5
A kind of UV-curable waterborne polyurethane resin of the present embodiment, its raw material and preparation method are as follows:
1) under nitrogen protection, by 27 part 1,6- hexamethylene diisocyanates are placed in and are leaked equipped with mechanical agitator, dropping liquid
In the four-hole boiling flask of bucket and reflux condensing tube, 30~40 DEG C are warming up to, start that 2 parts of castor oil and 0.0004 part of tin dilaurate is added dropwise
Dibutyl tin, 1.5~2h is reacted after dripping off at 50 ± 2 DEG C.
2) at being 50~55 DEG C in temperature, molten 0.0053 part 28 parts of polyether Glycols for having dibutyl tin laurate are added dropwise
(molecular weight is 1000g/mol), is dripped in 1h, and 75~80 DEG C are warming up to after dripping off, and reacts 2~2.5h.
3) 40~50 DEG C are cooled to, 3 parts of BDOs and 6 parts of epoxy acrylates dissolved with a small amount of acetone is added dropwise,
Completion of dropping in 1h.Rise high-temperature to 70~75 DEG C of 1~1.5h of reaction.
4) 40~50 DEG C are cooled to, then 7 parts of 2,2- dihydromethyl propionic acids (DMPA) are dissolved in a small amount of 1-METHYLPYRROLIDONE,
Disposably it is added directly into reactor, rises high-temperature to 70~75 DEG C of 2~2.5h of reaction, it is a small amount of by adding in course of reaction
Acetone obtains carboxylic base polyurethane prepolymer for use as to control the viscosity of reaction system.
5) 40~50 DEG C are cooled to, while stirring toward being added dropwise dissolved with polymerization inhibitor (4- hydroxyl -2,2,6,6- in above-mentioned performed polymer
Tetramethyl piperidine -1- oxygen radicals, 0.004 part) 15 parts of pentaerythritol triacrylates (PETA), dripped in 1h;Drop
60~70 DEG C are warming up to after adding, 0.0045 part of small molecule monohydric alcohol (absolute ethyl alcohol) end capping reaction 0.5 is added after 2~3h of reaction
~1h, then determines the content (use di-n-butylamine method) of isocyano, and terminating reaction after-NCO content is less than 0.2wt.% is obtained
To the castor oil and epoxy polyurethane modified urethane acrylate performed polymer of unsaturated acrylate ended.
6) less than 40 DEG C are cooled to, add 5 parts of triethylamines and 7 parts of deionized waters to carry out into salt breast toward above-mentioned performed polymer
Change, stirring reaction 1h obtains castor oil and epoxy polyurethane modified water-soluble UV resins under 1200r/min speed, pH value control exists
7.0 or so, its solid content is 85%.
In above-mentioned steps, the component is required to strict water removal.
Embodiment 6
A kind of UV-curable waterborne polyurethane resin of the present embodiment, its raw material and preparation method are as follows:
1) under nitrogen protection, by 33 parts of IPDIs be placed in equipped with mechanical agitator, dropping funel and
In the four-hole boiling flask of reflux condensing tube, 30~40 DEG C are warming up to, start that 2 parts of castor oil and 0.0004 part of fourth of tin dilaurate two is added dropwise
Ji Xi, 1.5~2h is reacted after dripping off at 50 ± 2 DEG C.
2) at being 50~55 DEG C in temperature, molten 0.0055 part 25 parts of polyether Glycols for having dibutyl tin laurate are added dropwise
(molecular weight is 1000g/mol), is dripped in 1h, and 75~80 DEG C are warming up to after dripping off, and reacts 2~2.5h.
3) 40~50 DEG C are cooled to, 3 parts of BDOs and 5 parts of epoxy acrylates dissolved with a small amount of acetone is added dropwise,
Completion of dropping in 1h.Rise high-temperature to 70~75 DEG C of 1~1.5h of reaction.
4) 40~50 DEG C are cooled to, then 6 parts of 2,2- dihydromethyl propionic acids (DMPA) are dissolved in a small amount of 1-METHYLPYRROLIDONE,
Disposably it is added directly into reactor, rises high-temperature to 70~75 DEG C of 2~2.5h of reaction, it is a small amount of by adding in course of reaction
Acetone obtains carboxylic base polyurethane prepolymer for use as to control the viscosity of reaction system.
5) 40~50 DEG C are cooled to, while stirring toward being added dropwise dissolved with polymerization inhibitor (hydroquinones, 0.004 in above-mentioned performed polymer
Part) 13 parts of pentaerythritol triacrylates (PETA), dripped in 1h;It is warming up to 60~70 DEG C after dripping, reaction 2~
Added after 3h, 0.0045 part of small molecule monohydric alcohol (absolute ethyl alcohol) 0.5~1h of end capping reaction, then determine the content of isocyano
(using di-n-butylamine method), terminating reaction after-NCO content is less than 0.2wt.%, obtains the castor-oil plant of unsaturated acrylate ended
Oil and epoxy polyurethane modified urethane acrylate performed polymer.
6) less than 40 DEG C are cooled to, add 6 parts of triethanolamines and 6 parts of deionized waters to carry out into salt breast toward above-mentioned performed polymer
Change, stirring reaction 1h obtains castor oil and epoxy polyurethane modified water-soluble UV resins under 1300r/min speed, pH value control exists
7.0 or so, its solid content is 82%.
In above-mentioned steps, the component is required to strict water removal.
Comparative example 1
A kind of UV-curable waterborne polyurethane resin of this comparative example, its raw material and preparation method similar embodiment 1, difference
It is:It is provided without the epoxy acrylate.
Comparative example 2
A kind of UV-curable waterborne polyurethane resin of this comparative example, its raw material and preparation method similar embodiment 1, difference
It is:It is provided without the castor oil.
Embodiment 7
The UV-curable waterborne polyurethane resin that embodiment 1-6 and comparative example 1-2 are prepared is respectively according to such as table 1
Formula is made aqueous polyurethane coating.
Table 1
Raw material | Consumption |
UV-curable waterborne polyurethane resin/g | 10 |
Pentaerythritol triacrylate/g | 0.05 |
Phosphate adhesion promoter/g | 0.15 |
Light trigger 1173/g | 0.4 |
Levelling agent/g | 0.1 |
Defoamer/g | 0.03 |
Water/g | 3 |
The preparation method of above-mentioned aqueous polyurethane coating is:It is accurate to weigh each component raw material according to formula, dispersed with stirring, i.e.,
, wherein, the levelling agent, defoamer can be using the conventional kinds of this area.
To aqueous obtained in the UV-curable waterborne polyurethane resin that is prepared as embodiment 1-6 and comparative example 1-2
Polyurethane coating carries out performance detection, and detection method is:Aqueous polyurethane coating is coated on tinplate, then the baking for being placed on 80 DEG C
Case dries 10min, then solidification (the suggestion curing light intensity 400mJ/cm on photo solidification machine2, 20m/s speed), can obtain solidified paint
Film;Test result is as shown in table 2:
Table 2
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of UV-curable waterborne polyurethane resin, it is characterised in that in parts by weight, including the following raw material component:
2. UV-curable waterborne polyurethane resin according to claim 1, it is characterised in that in parts by weight, including
The following raw material component:
3. UV-curable waterborne polyurethane resin according to claim 1, it is characterised in that the molecule of the polyalcohol
It is 500~1500g/mol to measure.
4. UV-curable waterborne polyurethane resin according to claim 3, it is characterised in that the polyalcohol is polyethers
One or more in dihydroxylic alcohols, PTMG dihydroxylic alcohols, polycaprolactone diols, PCDL.
5. UV-curable waterborne polyurethane resin according to claim 1, it is characterised in that the diisocyanate is
Isophorone diisocyanate, '-diphenylmethane diisocyanate, dicyclohexyl methyl hydride diisocyanate, toluene di-isocyanate(TDI), 1,
One or more in 6- hexamethylene diisocyanates.
6. UV-curable waterborne polyurethane resin according to claim 1, it is characterised in that the epoxy acrylate
Molecular weight be 450~460g/mol, solid content is 100%.
7. the UV-curable waterborne polyurethane resin according to claim any one of 1-6, it is characterised in that the catalysis
Agent is dibutyl tin laurate;The polymerization inhibitor be 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radicals, 2,2,6,
One or more in 6- tetramethyl piperidine -1- oxygen radicals, hydroquinones;The end-capping reagent is monohydric alcohol.
8. the UV-curable waterborne polyurethane resin according to claim any one of 1-6, it is characterised in that also including weight
Amount part is 4~5 parts of tertiary amine, and 6~8 parts of water.
9. the preparation method of the UV-curable waterborne polyurethane resin described in any one of claim 1-8, it is characterised in that bag
Include following steps:
(1) preparation of carboxylic base polyurethane prepolymer for use as:
Castor oil and partial catalyst are added in the diisocyanate, 1.5~2h is reacted in 45~55 DEG C;
Then the polyalcohol for being dissolved with the remaining catalyst is added in reaction solution, 75~80 DEG C of 2~2.5h of reaction are warming up to;
Then 40~50 DEG C are cooled to, the BDO and epoxy acrylate are added in reaction solution, then be warming up to 70
~75 DEG C of 1~1.5h of reaction;
Then 40~50 DEG C are cooled to, 2, the 2- dihydromethyl propionic acids are added in reaction solution, then be warming up to 70~75 DEG C instead
2~2.5h is answered, the carboxylic base polyurethane prepolymer for use as is obtained;
(2) preparation of UV-curable waterborne polyurethane resin:
After the carboxylic base polyurethane prepolymer for use as is cooled into 40~50 DEG C, is added in reaction solution and be dissolved with the polymerization inhibitor
Pentaerythritol triacrylate, be warming up to 60~70 DEG C reaction 2~3h;
The end-capping reagent is subsequently adding, after NCO content is less than 0.2wt%, terminating reaction obtains final product the UV-curable waterborne
Polyurethane resin.
10. a kind of aqueous polyurethane coating, it is characterised in that by weight percentage, including following component:
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CN114560993A (en) * | 2022-03-15 | 2022-05-31 | 阜阳师范大学 | Preparation method of chalcone-terminated photosensitive waterborne polyurethane/epoxy acrylate |
CN114560993B (en) * | 2022-03-15 | 2023-08-15 | 阜阳师范大学 | Preparation method of chalcone-terminated photosensitive waterborne polyurethane/epoxy acrylate |
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